IP Library Granted Patent US 8,716,198
Granted Patent B2
US 8,716,198 · App. 13/051,417 · Granted May 6, 2014

Prevention and remediation of water and condensate blocks in wells

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Quick Facts
Patent No.
US 8,716,198
App. No.
13/051,417
Granted
May 6, 2014
Kind
B2
Abstract

The present invention relates to a method of removing and preventing water and condensate blocks in wells by contacting a subterranean formation with a composition comprising a low molecular weight fluorinated copolymer having perfluoro alkyl moieties which are no longer than C 6 . A fluorinated copolymer of low molecular weight of about 50,000 g/mol and a method of preparing the same are also disclosed.

Claims (78)

1. A comprising the step of contacting a subterranean formation penetrated by a well bore to prevent or remove water block and/or condensate block with an aqueous composition comprising a fluorinated copolymer copolymerized from monomers comprising:

(a) from about 30 wt % to about 90 wt % of at least one monomer of formula I:

R f -Q-A-C(O)—C(R)═CH 2   I

wherein

R f is a straight or branched-chain perfluoroalkyl group of from 2 to 6 carbon atoms,

R is H or CH 3 ,

A is O, S or N(R′), wherein R′ is H or an alkyl of from 1 to about 4 carbon atoms,

Q is alkylene of 1 to about 15 carbon atoms, hydroxyalkylene of 3 to about 15 carbon atoms, —(C n H 2n )(OC q H 2q ) m —, —SO 2 —NR′(C n H 2n )—, or —CONR′(C n H 2n )—, wherein R′ is H or an alkyl of from 1 to about 4 carbon atoms, n is 1 to about 15, q is 2 to about 4, and m is 1 to about 15;

(b) from about 10 wt % to about 70 wt % of at least one monomer or a mixture of monomers is selected from formula IIA, formula IIB, or formula IIC:

(R 1 ) 2 N—(CH 2 ) r —Z—C(O)—C(R 2 )═CH 2   IIA

(O)(R 3 )(R 4 )N—(CH 2 ) r —Z—C(O)—C(R 2 )═CH 2   IIB

X − (R 5 )(R 4 )(R 3 )N + —(CH 2 ) r —Z—C(O)—C(R 2 )═CH 2   IIC

wherein

Z is —O— or —NR 5 —; R 1 is an alkyl group of from 1 to about 3 carbon atoms; R 2 is H or an alkyl radical of 1 to about 4 carbon atoms; R 3 and R 4 are each independently an alkyl of 1 to 4 carbon atoms, hydroxyethyl, benzyl, or R 3 and R 4 together with the nitrogen atom form a morpholine, pyrrolidine, or piperadine ring; R 5 is H or an alkyl of 1 to 4 carbon atoms, or R 3 , R 4 and R 5 together with the nitrogen atom form a pyridine ring; r is 2 to 4; provided that for formula IIA the nitrogen is from about 40% to 100% salinized; and

(c) from 0 wt % to about 7 wt % of a monomer of the formula III, IV, V or VI or a mixture thereof:

CH 2 (O)CH 2 —CH 2 —O—C(O)—C(R 2 )═CH 2   III;

Cl—CH 2 —CH(OH)CH 2 —O—C(O)—C(R 2 )═CH 2   IV;

(R 6 )OC(O)C(R 6 )═CH 2   V;

or

CH 2 ═CCl 2   VI

wherein

each R 2 is independently H or an alkyl radical of 1 to about 4 carbon atoms, and each R 6 is independently H or an alkyl of 1 to about 8 carbon atoms,

wherein fluorinated copolymer has an average molecular weight less than about 20,000g/mol, and wherein any perfluoroaliky moieties present in the fluorinated copolymer are no larger than 6 carbon atoms long.

2. The method of claim 1 wherein the fluorinated copolymer has an average molecular weight less than about 10,000 g/mol.

3. The method of claim 1 wherein the monomer of formula I is represented by CF 3 CF 2 (CF 2 ) x C 2 H 4 OC(O)—C(H)═CH 2 wherein x=0, 2, and 4.

4. The method of claim 1 wherein the fluorinated copolymer incorporates a monomer selected from formula IIA wherein the monomer selected is 2-methyl-, 2-(diethylamino)ethyl ester.

5. The method of claim 1 wherein the fluorinated copolymer incorporates a monomer selected from formula V wherein the monomer selected is 2-propenoic acid.

6. The method of claim 1 wherein the fluorinated copolymer is copolymerized from monomers consisting of:

(a) from about 30 wt % to about 90 wt % of at least one monomer of formula I:

R f -Q-A-C(O)—C(R)═CH 2   I

wherein

R f is a straight or branched-chain perfluoroalkyl group of from 2 to 6 carbon atoms,

R is H or CH 3 ,

A is O, S or N(R′), wherein R′ is H or an alkyl of from 1 to about 4 carbon atoms,

Q is alkylene of 1 to about 15 carbon atoms, hydroxyalkylene of 3 to about 15 carbon atoms, —(C n H 2n )(OC q H 2q ) m —, —SO 2 —NR′(C n H 2n )—, or

—CONR′(C n H 2n )—, wherein R′ is H or an alkyl of from 1 to about 4 carbon atoms, n is 1 to about 15, q is 2 to about 4, and m is 1 to about 15;

(b) from about 10 wt % to about 70 wt % of at least one monomer or a mixture of monomers selected from formula IIA, formula IIB, or formula IIC:

(R 1 ) 2 N—(CH 2 ) r —Z—C(O)—C(R 2 )═CH 2   IIA

(O)(R 3 )(R 4 )N—(CH 2 ) r —Z—C(O)—C(R 2 )═CH 2   IIB

X − (R 5 )(R 4 )(R 3 )N + —(CH 2 ) r —Z—C(O)—C(R 2 )═CH 2   IIC

wherein

Z is —O— or —NR 5 —; R 1 is an alkyl group of from 1 to about 3 carbon atoms; R 2 is H or an alkyl radical of 1 to about 4 carbon atoms; R 3 and R 4 are each independently an alkyl of 1 to 4 carbon atoms, hydroxyethyl, benzyl, or R 3 and R 4 together with the nitrogen atom form a morpholine, pyrrolidine, or piperadine ring; R 5 is H or an alkyl of 1 to 4 carbon atoms, or R 3 , R 4 and R 5 together with the nitrogen atom form a pyridine ring; r is 2 to 4; provided that for formula IIA the nitrogen is from about 40% to 100% salinized; and

(c) from 0 wt % to about 7 wt % of a monomer of the formula III, IV, V or VI or a mixture thereof:

CH 2 (O)CH 2 —CH 2 —O—C(O)—C(R 2 )═CH 2   III;

Cl—CH 2 —CH(OH)CH 2 —O—C(O)—C(R 2 )═CH 2   IV;

(R 6 )OC(O)C(R 6 )═CH 2   V;

or

CH 2 ═CCl 2   VI

wherein

each R 2 is independently H or an alkyl radical of 1 to about 4 carbon atoms, and each R 6 is independently H or an alkyl of 1 to about 8 carbon atoms.

7. The method of claim 6 wherein fluorinated copolymer has an average molecular weight less than about 10,000 g/mol.

8. The method of claim 6 wherein:

(a) the monomer of formula I is represented by CF 3 CF 2 (CF 2 ) x C 2 H 4 OC(O)—C(H)═CH 2 wherein x=0, 2, and 4;

(b) the fluorinated copolymer incorporates a monomer selected from formula IIA wherein the monomer selected is 2-methyl-, 2-(diethylamino)ethyl ester; and

(c) the fluorinated copolymer incorporates a monomer selected from formula V wherein the monomer selected is 2-propenoic acid.

9. The method of claim 1 , wherein the monomers of the fluorinated copolymer are copolymerized in the presence of dodecyl mercaptan.

10. A method for preventing or removing water block and/or condensate block in a subterranean formation penetrated by a well bore comprising the step of contacting the formation with an aqueous composition comprising a fluorinated copolymer copolymerized from monomers comprising:

(a) from about 30 wt % to about 90 wt % of at least one monomer of formula I:

R f -Q-A-C(O)—C(R)═CH 2   I

wherein

R f is a straight or branched-chain perfluoroalkyl group of from 2 to 6 carbon atoms,

R is H or CH 3 ,

A is O, S or N(R′), wherein R′ is H or an alkyl of from 1 to about 4 carbon atoms,

Q is alkylene of 1 to about 15 carbon atoms, hydroxyalkylene of 3 to about 15 carbon atoms, —(C n H 2n )(OC q H 2q ) m —, —SO 2 6—NR′(C n H 2n )—, or —CONR′(C n H 2n )—, wherein R′ is H or an alkyl of from 1 to about 4 carbon atoms, n is 1 to about 15, q is 2 to about 4, and m is 1 to about 15;

(b) from about 10 wt % to about 70 wt % of at least one monomer or a mixture of monomers is selected from formula IIA, formula IIB, or formula IIC:

(R 1 ) 2 N—(CH 2 ) r —Z—C(O)—C(R 2 )═CH 2   IIA

(O)(R 3 )(R 4 )N—(CH 2 ) r —Z—C(O)—C(R 2 )═CH 2   IIB

X − (R 5 )(R 4 )(R 3 )N + —(CH 2 ) r —Z—C(O)—C(R 2 )═CH 2   IIC

wherein

Z is —O— or —NR 5 —; R 1 is an alkyl group of from 1 to about 3 carbon atoms; R 2 is H or an alkyl radical of 1 to about 4 carbon atoms; R 3 and R 4 are each independently an alkyl of 1 to 4 carbon atoms, hydroxyethyl, benzyl, or R 3 and R 4 together with the nitrogen atom form a morpholine, pyrrolidine, or piperadine ring; R 5 is H or an alkyl of 1 to 4 carbon atoms, or R 3 , R 4 and R 5 together with the nitrogen atom form a pyridine ring; r is 2 to 4; provided that for formula IIA the nitrogen is from about 40% to 100% salinized; and

(c) from 0 wt % to about 7 wt % of a monomer of the formula III, IV, V or VI or a mixture thereof:

CH 2 (O)CH 2 —CH 2 —O—C(O)—C(R 2 )═CH 2   III;

Cl—CH 2 —CH(OH)CH 2 —O—C(O)—C(R 2 )═CH 2   IV;

(R 6 )OC(O)C(R 6 )═CH 2   V;

or

CH 2 ═CCl 2   VI

wherein

each R 2 is independently H or an alkyl radical of 1 to about 4 carbon atoms, and each R 6 is independently H or an alkyl of 1 to about 8 carbon atoms, wherein the fluorinated copolymer has an average molecular weight less than about 50,000 g/mol, and wherein any perfluoroalky moieties present in the fluorinated copolymer are no larger than 6 carbon atoms long.

Assignments (5)
SECURITY INTEREST Recorded Apr 4, 2018
From: THE CHEMOURS COMPANY FC, LLC
To: JPMORGAN CHASE BANK, N.A., AS ADMINISTRATIVE AGENT
Reel/Frame 045846/0011 →
RELEASE OF SECURITY INTEREST Recorded Apr 4, 2018
From: JPMORGAN CHASE BANK, N.A., AS ADMINISTRATIVE AGENT
To: THE CHEMOURS COMPANY FC, LLC
Reel/Frame 045845/0913 →
SECURITY AGREEMENT Recorded Jun 10, 2015
From: THE CHEMOURS COMPANY FC LLC; THE CHEMOURS COMPANY TT, LLC
To: JPMORGAN CHASE BANK, N.A.
Reel/Frame 035839/0675 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Apr 15, 2015
From: E. I. DU PONT DE NEMOURS AND COMPANY
To: THE CHEMOURS COMPANY FC, LLC
Reel/Frame 035432/0023 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Jun 8, 2011
From: IACONELLI, CHERYL LYNN; MARTIN, CHRISTOPHER JAMES; BROWN, GERALD ORONDE; ACOSTA, ERICK J.
To: E. I. DU PONT DE NEMOURS AND COMPANY
Reel/Frame 026408/0811 →